Amidoöxybenzyl compound and process of making same.



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ARTHUR EIOHENGRUN AND KARL DEMELER, OF ELBERFELD, GERMANY, ASSIGNORS TOFARBENFABRIKEN OF ELBERFELD CO., OF NElV YORK, N. Y., A CORPORATION OFNElV YORK.

AMIDOllXYBENZYL COMPOUND AND PROCESS OF MAKING SAME.

EPEGIFZQATiUIT forming part of Letters Patent No. 695,020, dated March25, 1902.

Application filed August 5,1901. S i N 7 p imens To all whom/ 15 mayconcern.-

Be it known that we, ARTHUR EIcHENcRiiN and KARL DEMELER, doctors ofphilosophy, chemists, residing at Elberfeld, Germany,

(assignors to the FARBENFABRIKEN on En BERFELD (30., of New York,) haveinvented a new and useful Improvement in New Chemical Bodies andProcesses of Making Same; and we hereby declare the following to be aclear and exact description of our invention.

To have found that new amido compounds having the following generalformula on,on c rr -on NH,

(in which formula R means hydrogen, an

alkyl or acidyl radical, such as methyl, ethyl,

acetyl, or the like,) can be obtained by first 2o treating nitrophenolswith the so-called halogen methylic alcohols, having the formulae CHOlOH, OH B1-OI-I, OH JOH- thatis to say,

the reaction products from formic aldehyde or substances which arecapable of yielding formic aldehyde and from haloid acids, such as H01,HJ, BrHin the presence of suitable condensing agents; secondly, treatingthe resulting derivatives of nitrophenols containing the group OH X (Xmeaning a halogen o atom) with hot water, alcohols, organic acids,

or the alkaline salts of these acids,and, finally,

reducing the so-produced nitrooxybenzyl alcohols, their ethers, andesters. The new bodies thus obtained are crystalline compounds readilysoluble in dilute mineral acids and in diluted solutions of causticalkalies and carbonates of alkalies, soluble in alcohol and soluble withdifficulty in water and ether.

They form salts with caustic alkalies and with mineral acids. At presentwe find that the new bodies are of especial value as photographicdevelopers.

In carrying out the new process practically we can proceed as follows,the parts being by 5 weight: Five parts of zinc chlorid are added to asolution of ten parts of paranitrophenol in eight parts of chloromethylalcohol. The

mixture turns hot spontaneously. After about twenty-four hours the newcompound precipitated in the mixture during the reaction is filtered offand purified by a recrystallizatiou from benzene. It represents smallneedles melting at about 132 centigrade. Subsequently a mixture preparedfrom the chloromethylic-para-nitrophenol thus obtained and the tenfoldquantity of water is heated for some time until a clear solutionresults. From the filtered liquid the new product having the formulaOI-LOII o r-1, 011

\No, precipitates 011 cooling in the shape of crystals melting at about128 centigrade. In order to reduce the said body, two parts of tin areadded to a mixture of one part of nitroparaoxybenzyl alcohol and tenparts of concentrated hydrochloric acid. The reaction goes on quietlyand can be accelerated by heating. After cooling the double salt of tinof the new amidoparaoxybenzyl alcohol separates. It is dissolved inwater and decomposed by a solution of sodium carbonate. The freeamidoparaoxybenzyl alcohol is dissolved in other, from which solution itis obso tained in a solid state.

The new base having the formula OH OH O H Ol-l NH represents colorlessleaves which are decomposed in contact with the air, soluble in hotwater, in alcohol, and in ether, melting at It forms salts The hydrofrom135 to 142 centigrade. with alkalies and with acids.

chlorid forms white needles which are stable.

The process proceeds in an analogous manner if other nitropl1enols-viz.,orthonitrophenol-are employed, or if the others and esters ofnitrooxybenzyl alcohols are reduced. The corresponding amido compoundobtained from nitroparaoxybenzylmethyl ether having the formula OH OOH Oi-I -OH represents slightly-yellowish leaves melting by first treatingnitrophenols with the socalled halogen methylic alcohols in the presenceof suitable condensing agents, secondly treating the resultingderivatives of nitrophcnols with water, alcohols, organic acids or thealkaline salts of these acids and finally reducing the so-producednitrooxybenzyl alcohols their ethers and esters, substantially ashereinbefore described.

2. The process for producing a new product having the formula 01-1 011 CH OH by first treating para-nitrophenol with chloromethylic alcohol,secondly heating the resulting chloromethylparanitrophenol with waterand finally reducing the paranitrooxybenzyl alcohol thus produced,substantially as hereinbefore described. 4 3. The herein described newamido compounds which are crystalline substances readily soluble indilute acids and in diluted solutions of caustic alkalies and carbonatesof alkalies,soluble in alcohol and soluble with difficultyin water andin ether, forming salts with alkalies and with mineral acids,substantially as hereinbefore described.

4. Theherein-describedamidoparaoxybenzyl alcohol having the formulawhich represents in free state colorless leaves which are decomposed incontact with the air, soluble in hot Water, alcohol and ether, formingsalts with caustic alkalies and acids and having the melting-point of135 to 142 centigrade and which as hydrochlorid forms white needles,substantially as hereinbefore described.

In testimony whereof we have signed our names in the presence of twosubscribing witnesses.

ARTHUR EICHENGRUN. KARL DEMELER.

Witnesses:

OTTO KoNIe, FRITZ ALBERS.

